Kinetic resolution of sulfur-stereogenic sulfoximines by Pd(ii)–MPAA catalyzed C–H arylation and olefination† † Electronic supplementary information (ESI) available: Copies of the 1H NMR, 13C NMR and HRMS data for all products. CCDC 2088890 and 2109210. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/d1sc04299h

ABSTRACT: A direct Pd(ii)-catalyzed kinetic resolution of heteroaryl-enabled sulfoximines through an ortho-C–H alkenylation/arylation of arenes has been developed. The coordination of the sulfoximine pyridyl-motif and the chiral amino acid MPAA ligand to the Pd(ii)-catalyst controls the enantio-discriminating C(aryl)–H activation. This method provides access to a wide range of enantiomerically enriched unreacted aryl-pyridyl-sulfoximine precursors and C(aryl)–H alkenylation/arylation products in good yields with high enantioselectivity (up to >99% ee), and selectivity factor up to >200. The coordination preference of the directing group, ligand effect, geometry constraints, and the transient six-membered concerted-metalation–deprotonation species dictate the stereoselectivity; DFT studies validate this hypothesis. A Pd/MPAA catalysed KR of heteroaryl substituted sulfoximines through C–H alkenylation and arylation (up to >99% ee) is developed. In-depth DFT studies uncover the salient features.

SUBMITTER: Mukherjee K 

PROVIDER: S-EPMC8597855 | biostudies-literature |

REPOSITORIES: biostudies-literature